Patent Application
20250005312
The present disclosure generally relates to physical information storage units, and particularly to physical information storage units formed by 3D printing.
Physical information storage units such as QR codes provide machine readable optical images that contain information specific to a labeled item. In addition, information provided by such physical information storage units can include data such as location data, identification data, tracking data, and anti-counterfeiting data, among others. However, the manufacture of physical information storage units can be complicated and costly.
Digital light processing three dimensional (DLP 3D) printing is a vat polymerization technique that builds 3D components (parts) by curing layer-by-layer a resin using a digital light projector. And grayscale DLP 3D (g-DLP 3D) printing employs grayscale light patterns to obtain functionally graded materials. However, current resins provide limited ranges in stiffness and elasticity.
The present disclosure addresses these issues with the manufacture of physical information units, the resins for g-DLP 3D printing, and other issues related to g-DLP 3D printing.
In one form of the present disclosure, a 3D printed physical information storage unit includes a grayscale digital light processing (g-DLP) 3D printed monolithic component formed from a resin that includes a donor moiety, an acceptor moiety, a rigid moiety, a photoinitiator, and a photoabsorber. The g-DLP 3D printed monolithic component has a first portion with a first Young's modulus and a second portion with a second Young's modulus that is different than the first Young's modulus such that the g-DLP 3D printed monolithic component subjected to a predefined strain exhibits a strain field that provides a machine readable optical image.
In another form of the present disclosure, a 3D printed physical information storage unit includes g-DLP 3D printed monolithic component formed from a resin that includes a donor moiety selected from one of 2-hydroxyethyl acrylate, caprolactone acrylate, hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate, 1,3-dihydroxypropyl acrylate, N-hydroxyethyl acrylamide, and aliphatic urethane-based diacrylate. The resin also includes an acceptor moiety selected from one of aliphatic urethane-based diacrylate and 2-hydroxyethyl acrylate, a rigid moiety is selected from one of isobornyl acrylate, 4-acryloylmorpholine, methyl methacrylate, 2-hydroxyethyl methacrylate, and isobornyl methacrylate, a photoinitiator, and a photoabsorber. The g-DLP 3D printed monolithic component has a first portion with a first Young's modulus and a second portion with a second Young's modulus that is different than the first Young's modulus such that the g-DLP 3D printed monolithic component subjected to a predefined strain exhibits a strain field that provides a machine readable optical image.
In still another form of the present disclosure, a 3D printed physical information storage unit includes a g-DLP 3D printed monolithic component formed from a resin that includes a 2-hydroxyethyl acrylate donor moiety, an aliphatic urethane-based diacrylate acceptor moiety, an isobornyl acrylate rigid moiety, a photoinitiator, and a photoabsorber. The g-DLP 3D printed monolithic component has a first portion with a first Young's modulus and a second portion with a second Young's modulus that is different than the first Young's modulus such that the g-DLP 3D printed monolithic component subjected to a predefined strain exhibits a strain field that provides a machine readable optical image.
These and other features of the g-DLP 3D printed physical information storage units and their manufacture will become apparent from the following detailed description when read in conjunction with the figures and examples, which are exemplary, not limiting.
The present teachings will become more fully understood from the detailed description and the accompanying drawings, wherein:
It should be noted that the figures set forth herein are intended to exemplify the general characteristics of the present technology for the purpose of the description of certain aspects. The figures may not precisely reflect the characteristics of any given aspect and are not necessarily intended to define or limit specific forms or variations within the scope of this technology.
The present disclosure provides three dimensional (3D) printed physical information storage units, resins for single-vat single cure g-DLP 3D printing of physical information storage units, and 3D printing of physical information storage units. The resins have a composition that provides highly stretchable soft organogel portions and stiff thermoset portions within a single layer of printing such that a monolithic 3D printed component having one or more stretchable (elastic) soft organogel portions and one or more stiff thermoset portions, without the use or need of multiple vats of different resins, is provided.
The present disclosure also provides printed physical information storage units with one or more stretchable soft organogel portions and one or more stiff thermoset portions. And when the physical information storage units are subjected to or placed under a predefined stress (e.g., greater than or equal to a predefined load or stress value), the stretchable soft organogel portion(s) exhibit a relatively large amount of strain (also referred to herein as a “high strain region”) and the stiff thermoset portion(s) exhibit a relatively small amount of strain (also referred to herein as a “low strain region”). Accordingly, the 3D printed physical information storage units exhibit or have different strain regions storing information that is retrieved via digital image processing.
In some variations, a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits Young Moduli ranging from about 10 MPa to about 100 MPa. In at least one variation, a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits Young Moduli ranging from about 10 MPa to about 200 MPa. In some variations a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits Young Moduli ranging from about 10 MPa to about 300 MPa. And in at least one variation, a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits Young Moduli ranging from about 10 MPa to about 400 MPa or from about 10 MPa to about 478 MPa.
In some variations, a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits Young Moduli ranging from about 8 MPa to about 100 MPa. In at least one variation, a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits Young Moduli ranging from about 5 MPa to about 100 MPa. In some variations a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits Young Moduli ranging from about 2 MPa to about 100 MPa. And in at least one variation, a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits Young Moduli ranging from about 1 MPa to about 100 MPa or from about 0.5 MPa to about 100 MPa or from about 0.1 MPa to about 100 MPa.
In some variations, a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits Young Moduli ranging from about 5 MPa to about 200 MPa. In at least one variation, a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits Young Moduli ranging from about 2 MPa to about 200 MPa. In some variations a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits Young Moduli ranging from about 1 MPa to about 300 MPa. And in at least one variation, a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits Young Moduli ranging from about 0.5 MPa to about 400 MPa or from about 0.1 MPa to about 475 MPa.
In some variations, a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits an elastic elongation up to 100%. And in some variations, a monolithic structure manufactured with a g-DLP 3D printer using a resin according to the teachings of the present disclosure exhibits an elastic elongation up to 200%, up to 300%, up to 400%, up to 450%, or over 450%. Stated differently, a monolithic structure manufactured via g-DLP 3D printing using a resin according to the teachings of the present disclosure has at least one portion with low stiffness and high elasticity and at least one portion with high stiffness and high strength as described in greater detail below.
It should be understood that 3D printing allows for the fabrication of components and structures with geometric and material complexities beyond what is physically and/or economically possible with traditional manufacturing techniques such as casting, machining, cold working, hot working, among others. And new 3D printing capabilities have demonstrated use in functional applications or structures such as deployable structures, soft robotics, flexible electrical components, and biomimetic designs. However, many functional applications such as nature-like structures, airless tires, multi-stable absorbers, and 4D printing require the use of materials with vastly different properties. That is, such structures have or require different portions with very different mechanical and/or physical properties.
It should also be understood that DLP 3D printing is a high-speed and high-resolution printing method that has become increasingly popular in recent years. Digital light processing uses a projector to irradiate hundreds or thousands of thin layers of resin having predefined cross-sections of a solid component such that each thin layer is cured and the solid component is manufactured layer-by-layer. In a typical DLP printing process, a single resin vat is used, only z-direction motion of a build plate is needed to form a component, and photopolymerization (or photocuring) of the thin layers occurs in a few seconds. Accordingly, DLP 3D printing is one of the fastest 3D printing technologies. However, the use of a single resin vat makes DLP in general, not suitable for printing components with multiple material properties. Methods using multiple vats have been developed to print two or more materials by transferring a printed component between multiple vats. However, cross-contamination between multiple vats, switching between different resin vats and cleaning significantly slows down the printing speed.
In g-DLP printing, the local degree of monomer conversion (curing) is controlled by light intensity, which is manipulated at pixel level by an input grayscale image. For example, and with reference to
Referring to
In some variations, the at least one hydrogen bond donating monomer 152 (also referred to herein as “donator moiety 152”) is an acrylate monomer with one or more a side groups that include a free carbonyl (—C═O) group or primary, secondary, or tertiary amine side group on an acrylate. And in at least one variation, the at least one hydrogen bond accepting monomer 154 (also referred to herein as “acceptor moiety 154”) is an acrylate monomer with one or more side groups that include a free hydroxy (—OH), a primary or secondary amine (—N(H)—, e.g., a urethane (C(O)—N(H)—), or an imine (—N═). And the at least one rigid monomer 156 (also referred to herein as “rigid moiety 156”) can be an acrylate monomer with one or more side groups that include one or more of cyclohexyls, substituted cyclohexyls, bicyclic side groups (structure) such as isobornyl, norbornyl, and dicylcopentanyl, among others. In addition, the donator moiety 152 and/or the acceptor moiety 154 is an oligomer (e.g., aliphatic urethane-based diacrylate) that functions as crosslinker.
Non limiting examples of the at least one hydrogen bond donating monomer 152 include 2-hydroxyethyl acrylate (2-HEA), caprolactone acrylate, hydroxypropyl acrylate, 2,3-dihydroxypropyl acrylate, 1,3-dihydroxypropyl acrylate, N-hydroxyethyl acrylamide, and aliphatic urethane-based diacrylate. Non-limiting examples of the at least one hydrogen bond acceptor monomer 154 include aliphatic urethane-based diacrylate (AUD) and 2-HEA. And non-limiting examples of the at least one rigid monomer 156 include isobornyl acrylate (IOBA), 4-acryloylmorpholine, methyl methacrylate, 2-hydroxyethyl methacrylate, and isobornyl methacrylate.
In some variations, resins according to the teachings of the present disclosure (also referred to herein simply as “resin 150”) include between about 5 weight percent (wt. %) and about 35 wt. % of the at least one hydrogen bond donator monomer 152, and in at least one variation the resin 150 includes between about 10 wt. % and about 30 wt. % of the least one hydrogen bond donator monomer 152. And in some variations, the resin 150 includes between about 15 wt. % and about 25 wt. % of the least one hydrogen bond donator monomer 152. For example, in at least one variation the resin 150 includes about 20 wt. % of the least one hydrogen bond donator monomer 152.
In some variations the resin 150 includes between about 5 wt. % and about 35 wt. % of the at least one hydrogen bond acceptor monomer 154, and in at least one variation the resin 150 includes between about 10 wt. % and about 30 wt. % of the least one hydrogen bond acceptor monomer 154. And in some variations, the resin 150 includes between about 15 wt. % and about 25 wt. % of the least one hydrogen bond acceptor monomer 154. For example, in at least one variation the resin 150 includes about 20 wt. % of the least one hydrogen bond acceptor monomer 154.
In some variations the resin 150 includes between about 45 wt. % and about 75 wt. % of the at least one rigid monomer 156, and in at least one variation the resin 150 includes between about 50 wt. % and about 70 wt. % of the least one rigid monomer 156 of an overall composition of the resin 150. And in some variations, the resin 150 includes between about 55 wt. % and about 65 wt. % of the least one rigid monomer 156. For example, in at least one variation the resin 150 includes about 60 wt. % of the least one rigid monomer 156.
In some variations, the resin 150 includes a photoinitiator. For example, in some variations the resin includes between about 0.1 wt. % and about 2 wt. % of the photoinitiator, for example between about 0.4 wt. % and 1.6 wt. % of the photoinitiator or between about 0.7 wt. % and about 1.3 wt. % of the photoinitiator. In at least one variation the resin 150 includes about 1.0 wt. % of the photoinitiator. Non-limiting examples of the photoinitiator include photoinitiator 819 (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide) and camphorquinone.
In some variations, the resin 150 includes a photoabsorber. For example, in some variations the resin includes between about 0.01 wt. % and about 1 wt. % of the photoabsorber, for example between about 0.025 wt. % and 0.5 wt. % of the photoabsorber or between about 0.04 wt. % and about 0.1 wt. % of the photoabsorber. In at least one variation the resin 150 includes about 0.05 wt. % of the photoabsorber. Non-limiting examples of the photoabsorber include methylene, coccine, and tartrazine.
In an effort to better describe the resin 150, its properties, and its capabilities for manufacturing monolithic structures with a range of properties, and yet not to limit the scope of the present disclosure in any manner, one example composition of the resin 150 and numerous examples of monolithic structures and corresponding properties are discussed below.
The resin 150 was prepared by mixing monomers of 2-hydroxyethyl acrylate (Sigma-Aldrich, MO, USA), isobornyl acrylate (Sigma-Aldrich), and AUD (Ebecryl 8413, Allnex, GA, USA) with a weight ratio of 20:60:20. Then, 1 wt. % photoinitiator (Irgacure 819, Sigma-Aldrich) and 0.05 wt. % photo absorber (Sudan I, Sigma Aldrich) were added to the mixture of monomers.
Not being bound by theory, the IOBA and 2-HEA were included as linear chain builders and AUD as a crosslinker. The AUD is a viscous oligomer with high molecular weight aliphatic chains and urethane units, and forms H—N . . . O hydrogen bonds when interacting with 2-HEA and IOBA monomers. Also, the 2-HEA provides abundant —OH groups that form additional O—H . . . O hydrogen bonds.
At a low degree of curing (also known as “degree of cure” and referred to herein as “DoC”), the covalent network with the prevalent hydrogen bonds of the cured resin provides high stretchability in a rubbery state as illustrated in
Referring to
Designs of the g-DLP 3D printed components were sliced into image files with a thickness of 0.05 mm and then converted into grayscaled image files with a MATLAB script. The layer-by-layer approach was utilized at the optimized speed of 3 s/layer to print the designed 3D structures. The light intensity of the printer was calibrated with a photometer (ILT1400-A Radiometer, International Light Technologies Inc., MA, USA) before printing.
Uniaxial tension tests of the g-DLP 3D printed components were performed with a universal test machine (Insight 10, MTS Systems Corp., Eden Prairie, MN, USA) with a cross-head speed of 5 mm/min. Dynamic thermomechanical properties were conducted on a DMA machine (Q800, TA Instruments, New Castle, DE, USA) with a temperature ramped at a rate of 10° C./min. The degree of curing was determined using normalized FTIR (Nicolet iS50 spectrometer, Thermo Fisher Scientific, Waltham, MA, USA) peak intensity of the acrylate group present at 809 cm−1. Multiple tests were conducted for each sample to guarantee reproducibility.
It should be understood that the different material properties were defined by the grayscale level of the UV projection, which varied from 0% (full intensity, labeled as G0) to 100% (full dark, labeled as G100). The photopolymerization kinetics were studied with a photopolymerization (PP) model as disclosed by Vitale et al., “Interfacial Profile and Propagation of Frontal Photopolymerization Waves” Macromolecules 2015, 48 (1), 198-205, in order to analyze the correlation of depth-dependent DoC with light dose. Based on a slicing thickness of 50 μm, and using the theoretically predicted correlation from the PP model and experimental trials, a grayscale range from G0 level to G70 (70% darkness) was used to ensure a rapid printing speed and a good shape fidelity. At G0, the light intensity was 24.82 mW/cm2 and the DoC was 96% (determined by FTIR measurement) and at G70, the light intensity was 0.85 mW/cm2, and the DoC was 55%.
The mechanical properties for structures formed from the resin 150 using the g-DLP 3D printer and printed with the different grayscale levels were evaluated with uniaxial tensile tests, and the thermomechanical properties were determined. As shown in
The stiff monomer IOBA increased the Tg at high DoC and made the network stiff, which ensured the modulus contrast at different DoC.
Referring to
The g-DLP 3D printed physical information storage unit 200 includes a plurality of stretchable soft organogel portions 210 and a plurality of stiff thermoset portions 220 such that when the g-DLP 3D printed physical information storage unit 200 is subjected to a predefined load or stress, the stretchable soft organogel portions 210 exhibit more strain that the stiff thermoset portions 220. For example, and with reference to
In this manner, contrast between the high strain regions 210s and the low strain regions 220s are used to form or provide machine readable optical images that store data such as location data, identification data, tracking data, and anti-counterfeiting data, among others. Non-limiting examples of such machine readable optical images include QR code images, data matrix images, bar code images, fine strain field images, course strain filed images, binarized strain field images, among others.
The preceding description is merely illustrative in nature and is in no way intended to limit the disclosure, its application, or uses. As used herein, the phrase at least one of A, B, and C should be construed to mean a logical (A or B or C), using a non-exclusive logical “or.” It should be understood that the various steps within a method may be executed in different order without altering the principles of the present disclosure. Disclosure of ranges includes disclosure of all ranges and subdivided ranges within the entire range.
The headings (such as “Background” and “Summary”) and sub-headings used herein are intended only for general organization of topics within the present disclosure and are not intended to limit the disclosure of the technology or any aspect thereof. The recitation of multiple forms or variations having stated features is not intended to exclude other forms or variations having additional features, or other forms or variations incorporating different combinations of the stated features.
As used herein the terms “about” and “generally” when related to numerical values herein refers to known commercial and/or experimental measurement variations or tolerances for the referenced quantity. In some variations, such known commercial and/or experimental measurement tolerances are +/−10% of the measured value, while in other variations such known commercial and/or experimental measurement tolerances are +/−5% of the measured value, while in still other variations such known commercial and/or experimental measurement tolerances are +/−2.5% of the measured value. And in at least one variation, such known commercial and/or experimental measurement tolerances are +/−1% of the measured value.
As used herein, the terms “comprise” and “include” and their variants are intended to be non-limiting, such that recitation of items in succession or a list is not to the exclusion of other like items that may also be useful in the devices and methods of this technology. Similarly, the terms “can” and “may” and their variants are intended to be non-limiting, such that recitation that a form or variation can or may comprise certain elements or features does not exclude other forms or variations of the present technology that do not contain those elements or features.
The broad teachings of the present disclosure can be implemented in a variety of forms. Therefore, while this disclosure includes particular examples, the true scope of the disclosure should not be so limited since other modifications will become apparent to the skilled practitioner upon a study of the specification and the following claims. Reference herein to one aspect, or various aspects means that a particular feature, structure, or characteristic described in connection with a form or variation is included in at least one form or variation. The appearances of the phrase “in one variation” or “in one form” (or variations thereof) are not necessarily referring to the same form or variation. It should also be understood that the various method steps discussed herein do not have to be carried out in the same order as depicted, and not each method step is required in each form or variation.
The foregoing description of the forms or variations has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular form or variation are generally not limited to that particular form or variation, but, where applicable, are interchangeable and can be used in a selected form or variation, even if not specifically shown or described. The same may also be varied in many ways. Such variations should not be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.
While particular forms or variations have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended, are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.
